US3267156A - Production of dialkyl ethers - Google Patents
Production of dialkyl ethers Download PDFInfo
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- US3267156A US3267156A US129512A US12951261A US3267156A US 3267156 A US3267156 A US 3267156A US 129512 A US129512 A US 129512A US 12951261 A US12951261 A US 12951261A US 3267156 A US3267156 A US 3267156A
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- Prior art keywords
- alcohol
- olefin
- varying
- ethers
- percent
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title description 4
- 150000001983 dialkylethers Chemical class 0.000 title description 3
- 150000001336 alkenes Chemical class 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 150000002170 ethers Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 150000001298 alcohols Chemical class 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 11
- 239000003456 ion exchange resin Substances 0.000 description 10
- 229920003303 ion-exchange polymer Polymers 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 8
- 230000036571 hydration Effects 0.000 description 8
- 238000006703 hydration reaction Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000887 hydrating effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- -1 aryl olefin Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical group CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OCXNFVQUCDFUIG-UHFFFAOYSA-N propan-2-ol;prop-1-ene Chemical compound CC=C.CC(C)O OCXNFVQUCDFUIG-UHFFFAOYSA-N 0.000 description 1
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 3,267,156 PRODUCTION 0F DIALKYL ETHERS Waldemar H. Hansen, West Deptford Township, Gloucester County, N..l., assignor to Socony Mobil Oil Company, Inc, a corporation of New Yorlr No Drawing. Filed Aug. 7, 1961, Ser. No. 129,512 2 Claims. (Cl. 260-614) This invention relates to the manufacture of ethers. It is more particularly concerned with a process for producing dialkyl ethers by the dehydration of alcohols.
As is well known to those familiar with the art, ethers have been produced by hydrating olefins and by the dehydration of alcohols. It has been proposed to carry out the dehydration reaction in the presence of sulfuric acid. This method, however, requires expensive facilities for handling corrosive materials. It has also been proposed to dehydrate alcohols to ethers in the presence of refractory metal oxide catalysts, such as alumina. This type of operation requires relatively high temperature. Therefore, substantial amounts of the alcohol charge are decomposed into olefin and water.
In the production of ethers by hydration of olefins, solid inorganic catalysts have been proposed. These catalysts include silica-alumina, phosphoric acid on a clay support, tungsten oxide, etc. In general, such catalysts have been lacking in activity and in selectivity. The acidic ion exchange resins have been found to be more active for hydrating olefins to ethers. These resins become deactivated because of polymerization and condensation of impurities, such as allene, methyl acetylene, oxygenated hydrocarbons, etc. which are present in the hydrocarbon feed. As the resin catalysts are not easily regenerable, the useful life of the catalyst is shortened.
It has now been found that ethers can be produced by a method that is simple and commercially feasible. It has been discovered that alcohols can be dehydrated selectively to ethers, with minimum decomposition of alcohol to water and propylene, in the presence of acidic ion exchange resin catalysts. It has further been discovered that ethers can be produced elficiently from olefins by a two-step process wherein olefins are hydrated to alcohols in the presence of an inorganic catalyst in the first step,
and then the alcohols are dehydrated to ethers, in the second step, in the presence of acidic ion exchange resin catalysts.
Accordingly, it is an object of this invention to provide a process for producing ethers. Another object is to provide a process for producing ethers, wherein the useful catalyst life of acidic ion exchange catalysts is increased. A specific object is to provide a process for dehydrating alcohols into ethers in the presence of acidic ion exchange resin catalysts. Another specific object is to provide a two-step process wherein olefins are hydrated to alcohols and then the alcohols are dehydrated to ethers. Other objects and advantages of this invention will become apparent to those skilled in the art, from the following detailed description.
In general, this invention provides a process for producing ethers that comprises contacting a substantially anhydrous alcohol with an acidic ion exchange catalyst, in the absence of added water and olefin, at a temperature varying between about 250 F. and about 400 F., under a pressure varying between about 500 p.s.i.g. and about 1500 p.s.i.g., and at a liquid hourly space velocity varying between about 0.1 and about 4.
Another embodiment of this invention provides a twostep process for producingethers from olefins that comprises contacting an olefin and water with a solid, refractory inorganic hydration catalyst at a temeprature varying between about 350 F. and about 750 F., at an olefin partial pressure varying between about 500 p.s.i.g. and about 3000 p.s.i.g., using an olefin liquid hourly space velocity varying between about 0.3 and about 2, and using a molar ratio of water to olefin varying between about 1 and about 50; separating an alcohol product; and contacting said alcohol in a substantially anhydrous state with an acidic ion exchange resin catalyst, in the absence of added water and olefin, at a temperature varying between about 250 F. and about 400 F., under a pressure varying between about 500 p.s.i.g. and about 1500 p.s.i.g., and at a liquid 'hourly space velocity varying between about 0.1 and about 4.
The alcohol reactant for the dehydration of alcohol to ether is an alkauol having between 2 and 5 carbon atoms, inclusive. The alcohol reactant can be straight chained or branched chained. It is further contemplated to use mixtures of alcohols, which can include straight and branched chained alcohols or alcohols or varying chain length, or both. Non-limiting examples of the alcohols are ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, and isopentanol. With respect to the dehydration of alcohol to ether, as a process by itself, the source of the alcohol reactant is not a determinant factor. Thus, the alcohol reactant, in this respect, can be derived from any source, including commercial sources and synthesis by any of the means well known in the art. With regard to an embodiment of the present process, however, that features a two-step process of first hydrating an olefin to alcohol and dehydrating the alcohol to ether, the source of the alcohol reactant is important to the over-all process. The method for preparing alcohols by hydration of ole fins is discussed hereinafter.
However, with specific regard to the dehydration of alcohol, the catalyst found utilizable are the acidic organic ion exchange resins. These resins are in the acid form and contain free sulfonic, sulfuric, phosphoric, or phosphonic acid groups. The ion exchange resins contemplated herein are synthetic aryl resins, having essentially a hydrocarbon skeleton, combined with strong mineral acid groups. The strong mineral acid groups can be put into the aryl olefin monomer before it is polymerized, or the mineral acid groups can be put into the material after the polymerization.
Suitable resins include solid sulfonated cross-linked polymers of styrene that contains between about 6 percent and about 15 percent divinyl benzene. Such resins can be produced as described in United States Letters Patent No. 2,3 66,007. Further description of the preparation of acidic organic ion exchange resins and their use in hydrating olefins to alcohols and ethers can be found in United States Letters Patent No. 2,813,908.
The dehydration of alcohol to ether, in the presence of acidic organic ion exchange resins, is carried out at temperatures varying between about 250 F. and about 400 F., and preferably between about 250 F. and about 300 F. The pressure will be super atmospheric, i.e., between about pounds per square inch gauge (p.s.i.g.)
and about 1 500 p.s.i.g., and preferably between about 500 and about 1000 p.s.i.g. The LHSV (alcohol liquid volume per volume of catalyst per hour) will vary between about 0.3 and about 4, preferably between about 0.3 and about one.
The process of dehydration can be carried out batchwise or in a continuous process. The major products are ether, unreacted alcohol, and water. The alcohol when dried can be recycled.
As was mentioned hereinbef-ore, a two-step process is contemplated. In such a process, the first step involves the hydration of olefins to alcohols, followed by the second step of dehydrating the alcohol thus-produced to an ether, as aforedescribed.
The olefin feed to the hydration step is a monoolefin containing between 2 and carbon atoms. The olefin reactant can be relatively pure, or mixtures of olefins. It is also contemplated to use mixtures of olefins with the corresponding saturated hydrocarbon, such as propanepropylene, ethane-ethylene, and butane-butylene cuts. Non-limiting examples of the olefin reactant are ethylene, propylene, butylene, isobutylene, and amylene.
The refractory inorganic hydration catalysts are well known in the art. These include composites of silica and alumina, alumina impregnated with aluminum sulfate, phosphoric acid on clay, and tungsten oxide A preferred catalyst herein is comprised of 75 weight percent silica and 25 weight percent alumina.
As those familiar with the art will readily appreciate, the operating conditions for the hydration step will vary depending upon the particular olefin and catalyst used. In general, over a heterogeneous solid catalyst, the hydration will be carried out at temperatures varying between about 350 F. and about 750 F., and preferably at about 450 F. The mole ratio of water to olefin is between about 1 and about 50, preferably about 35. The olefin partial pressure is between about 500 and about 3,000 pounds per square inch gauge (p.s.i.g.) and preferably between about 1,000 and about 1,500 p.s.i.g. The olefin LHSV (liquid volume per volume catalyst per hour) will vary between about 0.3 and about 2, and preferably between about 0.3 and about 0.5. This reaction can be carried out batchwise, but a continuous process is preferred.
The alcohol can be separated from water by a two column azeotropic distillation using product ether as separating agent in the second distillation column. The alcohol can be dried with calcium chloride, molecular sieve, or using other conventional means.
DEHYDRATION TO ETHER Examples 1 and 2 at 300 F. and under a pressure of 500 p.s.i.g. Results I are set forth in Table I.
TABLE I Example l 1 I 2 Alcohol LHSV 0. 26 0. 52 Liquid Product Composition, percent:
Diisopropyl ether 32. 6 25. 3 Isopropyl alcohol 54. 3 60. 4 Water 13. 1 14. 3 Isopropyl alcohol conversion, percent 32. 6 24. 6
4. Examples 3 through 6 In order to show the effect of temperature, runs were made as described in Examples 1 and 2, except that the temperature was varied. In each run the pressure was 500 psig. and the LHSV was 0.5. Pertinent data for these runs on isopropyl alcohol are set forth in Table II.
TAB LE II Example u 3 I 4 5 l 6 Temperature, F 250 300 350 400 It will be noted from the data in Tables I and II that an alcohol can readily be converted into an ether by contacting it with an acidic organic ion exchange resin. Better yields are obtained at 250-300 F. (Examples 3 and 4), but these can be increased by lowering LHSV (Example 1). In any case, the unconverted alcohol can be recovered, dried, and recycled.
In another embodiment of this invention, an olefin can be hydrated to form the corresponding alcohol, which can be converted to the ether as aforedescribed. This is illustrated in the following examples.
Examples 7 through 9 TABLE III Percent Percent Propylene Isopropanol Example Temp., F. Conv. to in aqueous Isopropanol product oowro The alcohol produced in these runs is separated from the water, dried and charged to the ion exchange catalyst to produce the ether. Unconverted olefin and water can be recycled, with make-up olefin.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.
What is claimed is:
1. A process for producing ethers that comprises contactiug a substantially anhydrous alcohol having between 2 and 5 carbon atoms, inclusive, with a sulfonated resin copolymer of styrene and divinylbenzene containing between about 6 percent and about 15 percent divinylbenzene cross-linking agent, in the absence of added water and olefin, at a temperature varying between about 250 F. and about 400 F., under a pressure varying between about 500 p.s.i.g. and about 1500 p.s.i.g., and at a liquid hourly space velocity varying between about 0.1 and about 4.
2. A process for producing diisopropyl ether that comprises contacting substantially anhydrous isopropanol o with a sulfonated resin copolymer of styrene and divinylbenzene containing between about 6 percent and about 15 percent divinylbenzene cross-linking agent, in the absence of added water and olefin, at a temperature varying between about 250 F. and about 300 F., under a pressure varying between about 500 p.s.i.g. and about 1000 p.s.i.g., and at a liquid hourly space velocity varying between about 0.3 and about one.
References Cited by the Examiner UNITED STATES PATENTS 5/1956 Ehm et al 260-614 X 7/1958 Friedman et a1 260614 Brewster, Organic Chemistry, 2nd ed. (1953), 62-64, 132-134 (1953).
10 LEON ZITVER, Primary Examiner.
LORRAINE A. WEINBERGER, Examiner. B. HELFIN, Assistant Examiner,
Claims (1)
1. A PROCESS FOR PRODUCING ETHERS THAT COMPRISES CONTACTING A SUBSTANTIALLY ANHYDROUS ALCOHOL HAVING BETWEEN 2 AND 5 CARBON ATOMS, INCLUSIVE, WITH A SULFONATED RESIN COPOLYMER OF STYRENE AND DIVINYLBENZENE CONTAINING BETWEEN ABOUT 6 PERCENT, AND ABOUT 15 PERCENT DIVINYLBENZENE CROSS-LINKING AGENT, IN THE ABSENCE OF ADDED WATER AND OLEFIN, AT A TEMPERATURE VARYING BETWEEN ABOUT 250* F. AND ABOUT 400*F., UNDER A PRESSURE VARYING BETWEEN ABOUT 500 P.S.I.G. AND ABOUT 1500 P.S.I.G., AND AT A LIQUID HOURLY SPACE VELOCITY VARYING BETWEEN ABOUT 0.1 AND ABOUT 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US129512A US3267156A (en) | 1961-08-07 | 1961-08-07 | Production of dialkyl ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US129512A US3267156A (en) | 1961-08-07 | 1961-08-07 | Production of dialkyl ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3267156A true US3267156A (en) | 1966-08-16 |
Family
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|---|---|---|---|
| US129512A Expired - Lifetime US3267156A (en) | 1961-08-07 | 1961-08-07 | Production of dialkyl ethers |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299956A (en) * | 1980-09-17 | 1981-11-10 | Texaco Inc. | Method of making N-(2-methoxyethyl)morpholine |
| US4337366A (en) * | 1974-11-21 | 1982-06-29 | Snamprogetti S.P.A. | Method for the preparation of ethers |
| US4528406A (en) * | 1983-11-30 | 1985-07-09 | Atlantic Richfield Company | Production of bis(alpha-alkylbenzyl)ethers |
| EP0196902A2 (en) * | 1985-03-27 | 1986-10-08 | The British Petroleum Company p.l.c. | Process for the hydration and oligomerisation of olefins |
| US4935552A (en) * | 1989-01-12 | 1990-06-19 | Mobil Oil Corporation | Dual stage process for the production of ethers |
| US4969987A (en) * | 1989-11-29 | 1990-11-13 | Mobil Oil Corporation | Integrated process for production of gasoline and ether |
| US5047070A (en) * | 1988-04-11 | 1991-09-10 | Mobil Oil Corporation | Integrated process for production of gasoline and ether from alcohol with feedstock extraction |
| US5231234A (en) * | 1992-03-30 | 1993-07-27 | Chemical Research & Licensing Company | Two stage production of ether from tertiary alcohol |
| US5684213A (en) * | 1996-03-25 | 1997-11-04 | Chemical Research & Licensing Company | Method for the preparation of dialkyl ethers |
| US20090069607A1 (en) * | 2007-09-10 | 2009-03-12 | Catalytic Distillation Technologies | Method for the production of dimethyl ether |
| US20100179355A1 (en) * | 2007-09-05 | 2010-07-15 | E. I. Du Pont De Nemours And Company | Processes for making dialkyl ethers from alcohols |
| US20100197974A1 (en) * | 2007-09-05 | 2010-08-05 | E.I. Du Pont De Nemours And Company | Processes for making dialkyl ethers from alcohols |
| US20100197975A1 (en) * | 2007-09-05 | 2010-08-05 | E.I. Du Pont De Nemours & Company | Process for making dialkyl ethers from alcohols |
| US20100204521A1 (en) * | 2007-09-05 | 2010-08-12 | Mark Harmer | Processes for making dibutyl ethers from 2-butanol |
| US20100204522A1 (en) * | 2007-09-05 | 2010-08-12 | E. I. Du Pont De Nemours And Company | Process for making dibutyl ethers from isobutanol |
| EP3219371A1 (en) | 2016-03-14 | 2017-09-20 | Ineos Solvents Germany GmbH | Column tray for the reactive distillation of heteroazeotropes and process using the tray |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2746738A (en) * | 1952-10-28 | 1956-05-22 | Toledo Scale Co | Wheel load truck scale |
| US2845463A (en) * | 1955-06-10 | 1958-07-29 | Sinclair Refining Co | Production of alcohols and ethers |
-
1961
- 1961-08-07 US US129512A patent/US3267156A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2746738A (en) * | 1952-10-28 | 1956-05-22 | Toledo Scale Co | Wheel load truck scale |
| US2845463A (en) * | 1955-06-10 | 1958-07-29 | Sinclair Refining Co | Production of alcohols and ethers |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337366A (en) * | 1974-11-21 | 1982-06-29 | Snamprogetti S.P.A. | Method for the preparation of ethers |
| US4299956A (en) * | 1980-09-17 | 1981-11-10 | Texaco Inc. | Method of making N-(2-methoxyethyl)morpholine |
| US4528406A (en) * | 1983-11-30 | 1985-07-09 | Atlantic Richfield Company | Production of bis(alpha-alkylbenzyl)ethers |
| EP0196902A2 (en) * | 1985-03-27 | 1986-10-08 | The British Petroleum Company p.l.c. | Process for the hydration and oligomerisation of olefins |
| WO1986005776A1 (en) * | 1985-03-27 | 1986-10-09 | The British Petroleum Company P.L.C. | Process for the hydration and oligomerisation of olefins |
| EP0196902A3 (en) * | 1985-03-27 | 1987-01-21 | The British Petroleum Company p.l.c. | Process for the hydration and oligomerisation of olefins |
| US5047070A (en) * | 1988-04-11 | 1991-09-10 | Mobil Oil Corporation | Integrated process for production of gasoline and ether from alcohol with feedstock extraction |
| US4935552A (en) * | 1989-01-12 | 1990-06-19 | Mobil Oil Corporation | Dual stage process for the production of ethers |
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| EP3219371A1 (en) | 2016-03-14 | 2017-09-20 | Ineos Solvents Germany GmbH | Column tray for the reactive distillation of heteroazeotropes and process using the tray |
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